N,n-dimethylolcarbamates of ether alcohols



United States Patent 3 Claims ABSTRACT OF THE DISCLOSURE Compounds of the formula RO[CH2CH2O]I.CNH2CI;/NH2

wherein R is an alkyl group having 1 to 6 carbon atoms and n is an integer of 1 to 10, formaldehyde condensates thereof, methods of crease proofing cellulosic fabrics with such condensates, novel cellulosic fabrics having such condensates cured thereon, novel mixtures of such condensates and triazone-formaldehyde condensates, and r fabrics having such mixtures cured thereon.

This invention is directed to a novel class of carbamates, their condensation products with formaldehyde and the use of such condensation products in the treatment of cellulosic fabrics to impart crease resistance thereto.

Heretofore, various carbamates have been made and employed for providing wrinkle-resistant finishes to cellulosic fabrics. Arceneaux, Frick, Reid and Gautreaux of Southern Regional Research Laboratory reported in their article appearing on pages 37 through 41 of the American Dyestuff Reporter, Oct. 30, 1961, that ethylene bis- (N-methylolcarbamate) produced wrinkle resistance in cellulosic fabrics but imparted a high susceptibility to chlorine damage thereto. This defect was somewhat modified by these workers by replacing the nitrogen bonded hydrogen atoms of this compound with methyl groups. Arceneaux and Reid then reported in an article on pages 45 and 46 of the American Dyestuif Reporter of Oct. 15, 1962, that they had attempted to explain the lack of consistency in the use of carbamates in the treatment of cellulosic textiles. The use of carbamate based resins has not been commercially important up to the present time because of the difficulty in obtaining reproducible results and the undue damage due to chlorine retention. In other cases, heretofore known carbamate resins deteriorated the tensile and tear strength of the fabric. They also are volatile and produced undesirable odor levels.

It is, therefore, an object of this invention to provide novel carbamates which are useful in forming creaseproofing chemicals for cellulosic fabrics.

Another object is the production of novel cellulosic textile crease-proofing chemicals by condensing formaldehyde with novel carbamates.

Another object is the treatment of cellulosic textiles with condensation products of formaldehyde and novel carbamates.

Another object is the provision of cellulosic textiles treated with condensation products of formaldehyde and novel carbamates.

A further object is the provision of novel carbamateformaldehyde condensates which are useful in the treatment of cellulosic textiles to provide reproducible, superior results in crease resistance, low damage due to retained chlorine, little strength loss and low odor.

3,524,876 Patented Aug. 18, 1970 Further objects and advantages will be apparent from the following detailed description.

The novel carbamates of this invention have the following formula:

wherein R is an alkyl group having 1 to 6 carbon atoms and n is an integer of l to 10. Especially preferred carbamates of the present invention are those having the above formula wherein n is 1, i.e., compounds having the formula:

R0 CHzCHzO (NINE:

wherein R is an alkyl group having 1 to 6 carbon atoms. These novel carbamates are prepared by reacting urea with a monoalkyl ether of an ethylene glycol having 1 to 10 ethyleneoxy groups wherein the alkyl group contains 1 to 6 carbon atoms. Illustrative monoalkyl ethers include the monoethyl ether of ethylene glycol or Cellosolve, the monohexyl ether of ethylene glycol, the monomethyl ether of deca-ethylene glycol, the monobutyl ether of triethylene glycol, the monoisobutyl ether of tetraethylene glycol, and the like. The reaction with urea is preferably carried out at elevated temperatures, preferably above l00 C. The reaction is accompanied by the evolution of ammonia which can be used as an indication of the extent of reaction that has taken place at any given time. A high boiling solvent or diluent, such as glycerol, can be employed if desired. The resulting carbamate then can be purified by filtration, precipitation, crystallization and recrystallization.

The novel carbamates of the present invention include those having the above formula wherein R is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and the like, and wherein n is 1. The present invention relates to the following novel carbamates: ethoxyethyl carbamate, methoxyethyl carbamate, propoxyethyl carbamate, isopropoxyethyl carbamate, butoxyethyl carbamate, isobutoxyethyl carbamate, pentoxyethyl carbamate, hexoxyethyl carbamate.

N-dimethylolcarbamate, hexoxyethyl N,N-dimethylolcarbamate.

etc. Such resins or condensates are readily formed by reacting formaldehyde with the novel carbamates under alkaline conditions at moderately elevated temperatures, for example, up to 100 C.

Then the novel crease-proofing chemicals of this invention are conveniently applied to cellulosic textile fabrics as an aqueous solution having a solids content which can be varied over a wide range which, however, preferably would not extend below 2% nor above 80%. The aqueous treating solution can also contain other ingredients such as softeners, wetting agents, water repellents, soil repellents, and the like in addition to a suitable curing catalyst such as zinc nitrate, magnesium chloride, isopropanolamine hydrochloride or any other acidic salt catalyst or mixtures thereof. Any curing catalyst conventionally employed to cure nitrogenous crease-proofing chemicals can also be employed to cure the novel chemicals of this invention.

The aqueous treating solutions are applied to the cellulosic fabric and conventional techniques such as padding can be employed. The pick-up on the fabric can also vary over a wide range, e.g., wet pick-ups of 50 to 100 percent based on the Weight of the fabric.

After application to the fabric, the crease-proofing chemicals thus carried by the fabric are cured under suitable curing conditions such as at a curing temperature of 250 to 360 F. for 5 minutes to 1 minute. If desired, the fabric can be dried after application of the treating solution and prior to curing. While air drying at ambient temperatures can be employed, it is preferred and more expeditious to dry at elevated temperatures.

The fabric to be treated may be prepared in any desired manner such as by singeing, desizing, bleaching and other operations prior to impregnating with the novel creaseproofing chemical and catalyst according to the present invention. Substantially any type of cellulosic fabric can be treated according to this invention. For example, 100 percent cotton woven fabrics, cotton-synthetic fiber blends, 100 percent rayon, rayon-synthetic fiber blends, rayon-cotton blends, all can be treated in accordance with this invention to provide the advantages set forth hereinabove. The term synthetic or other fibers is intended to include rayon fibers, polyester fibers, such as Fortrel (registered trademark of Fiber Industries, Inc.), which is a polyester comprising a polymerized polycond'ensate of terephthalic anhydride and ethylene glycol; nylon; polymers containing at least 80 percent polymerized acrylonitrile, such as those available commercially under the trade names Orlon and Acrilan, and so on. Staple synthetic fibers, or continuous synthetic filaments, as desired, can be employed in the ways that are well known in the art. This invention, nevertheless, can be applied with advantage to any woven or knitted cellulosic fabric, with or without any amount of synthetic or other fibers. The term cellulosic textile fabric as used herein means any of the above-described fabrics, including blends which contain cellulosic fibers such as cotton, rayon and the like.

The formaldehyde condensates of the carbamates of this invention are also useful in admixture with formaldehyde-triazone condensates to provide crease-proofing mixtures of superior properties. Condensates of formaldehyde and triazones having the formula:

wherein R is alkyl or hydroxyalkyl having 1 to 4 carbon atoms have been employed for crease-proofing cellulosic textiles. The above triazone condensates may contain from 0 to 1.0 mole parts of urea formaldehyde condensate based on the combined urea in said urea formaldehyde condensate per mole part of triazone formaldehyde condensate.

The relative amounts of formaldehyde-triazone condensates, such as those described above, and novel formaldehyde-carbamate condensates employed in the novel mixtures of this invention can vary widely and preferably range from 0.05 to 1.5 weight parts of said formaldehydetriazone condensate per weight part of said formaldehydecarbamate condensate. Such mixtures are advantageously employed in aqueous solution in the manner described above.

These novel mixtures when used to crease-proof cellulosic fabrics result in crease-proofed fabrics of improved tear and tensile strength and consistently low chlorine retention damage. Such mixtures are also advantageous in reducing the sensitivity of formaldehyde-carbamate condensates to variations in processing conditions employed in impregnating and curing and lessen the possible adverse eflects of certain catalysts on certain dyestuffs.

The following examples are presented. Unless otherwise specified, the percentages and parts set forth in the examples are by Weight and the temperatures set forth are in degrees Fahrenheit. The crease-resistance values were determined by the Monsanto Crease Recovery Test (AATCC Tentative Test Method 66-1959T). Reflectance values were determined on a Hunter Model D-40 Reflectometer using a blue filter for "Reflectance B and using a green filter for Reflectance G. The values for percent damage or strength loss due to retained chlorine were obtained in accordance with AATCC Standard Test Method 921962. The filling tensile strength values were obtained in accordance with the Grab method and the filling tear strength values were obtained'in accordance with the Trapezoid method.

The formaldehyde odor was determined by the Dan River jar method using Schiifs reagent and a colorimeter or spectrophotometer. The method is designed to obtain comparative figures for the potential release of formaldehyde odor from resin-treated fabrics under simulated conditions of high heat and humidity such as the treated fabric may encounter in confined storage or similar environments. The method comprising suspending a weighed fabric sample over a fixed amount of water in a sealed mason jar, placing the jar in an oven for a specified time at a specified temperature and subsequently cooling the jar and determining, colorimetrically, the amount of formaldehyde absorbed by the Water in the bottom of the jar. Suitable aqueous solutions containing known concentrations of formaldehyde are used as standards.

The method covers the range from about 300 p.p.rn. on the weight of the fabric, which is undetectable by the human nose, to about 3500 p.p.m. which is very odoriferous.

EXAMPLE I A mixture containing 180 grams (2 mols) of the monoethyl ether of ethylene glycol and grams (2 mols) of urea was prepared at room temperature and heated to C. Thereafter, 12 grams of glycerol were added and heating continued while the temperature slowly rose as the reaction proceeded. The temperature was allowed to reach 170 to 175 C., at which time an additional grams of glycerol was added. The amount of heating was reduced to maintain the temperature within the range of 170 to 175 C. Ammonia was evolved during the entire reaction period and a small amount of ammonium carbonate was formed. The temperature was held at 170 to 175 C. for 4 hours to complete the reaction. A small amount of a gray powder was precipitated at the highest temperature and was presumed to be cyanuric acid. The reaction product was filtered while hot to remove the precipitate. Then the reaction product was cooled and acetone was added to precipitate any unreacted urea remaining. The reaction product was then filtered and the acetone was evaporated off to crystallize out ethoxyethyl carbamate. This carbamate was then recrystallized from ethanol to produce crystals having a melting point of 60 to 62 C.

A mixture was prepared containing 132 grams (about 1 mol) of ethoxyethyl carbamate prepared as described above and 194.4 grams (about 2.4 mols) of 37% aqueous formaldehyde (about 2.4 mols of formaldehyde). The resulting mixture was reacted at a pH of 10.5 for 30 minutes at 80 C. The resulting reaction product was an aqueous solution of ethoxyethyl N,N-dirnethylolcarbamate. This solution was adjusted to contain 50% solids by the addition of water.

An aqueous treating solution was prepared containing 12% of the 50% solids aqueous solution of ethoxyethyl N,N-dimethylolcarbamate and 3% of a 31.5% solids aqueous solution of zinc nitrate.

A second aqueous treating solution was prepared containing 12% of the 50% solids aqueous solution of ethoxyethyl N,N-dimethylolcarbamate prepared as described above and 3% of a 64% solids aqueous solution of magnesium chloride hexahydrate.

Each of the above solutions was applied to a 100% cotton fabric by padding to a 60% wet pick-up based on the weight of the fabric. Each impregnated fabric was air dried at ambient temperatures and then cured at 340 F. for 70 seconds. The resulting treated and cured fabrics had the following properties:

An aqueous treating solution is prepared containing 12% of the 50% solids aqueous solution of ethoxyethyl N,N-dimethylolcarbamate; 3% of an aqueous solution containing 31.5% solids zinc nitrate; 3.5% of a 47.4% solids aqueous solution of a resin mixture of 60 mol percent of N,N-di-methylol-5-hydroxyethyltetrahydro-s-triazone-2 and 40 mol percent of dimethylol urea and containing 5% excess formaldehyde. The aqueous solution is then applied to a 100% cotton fabric by padding to a 68% wet pick-up based on the weight of fabric. The impregnated fabric is oven dried at 300 F. for 56 seconds and then cured at 340 F. for 70 seconds. The resulting fabric has a high level of crease-resistance, little or no odor, excellent reflectance and exhibits a very low damage due to chlorine retention.

The above example is repeated utilizing, however, in place of the above-mentioned, 47.4% solids solution, 1.7% of a 69% solids aqueous solution containing 84 mol percent N,N' dimethylol 5 ethyltetrahydro-striazone- 2 and 16 mol percent dimethylol urea with 5% excess formaldehyde. The cured fabric resulting from this treatment possessed a high level of crease-resistance, a low odor, an excellent reflectance and very low damage due to retained chlorine.

The foregoing description is intended for purposes of illustration and not limitation inasmuch as obvious equivalents will be apparent to those skilled in the art without departing from the scope of this invention.

What is claimed is:

1. A compound of the formula:

wherein R is an alkyl group having 1 to 6 carbon atoms and n is an integer of 1 to 10.

2. A compound of the formula:

wherein R is an alkyl group having 1 to 6 carbon atoms.

3. Ethoxyethyl N,N-dimethylolcarbamate.

References Cited UNITED STATES PATENTS 1,927,858 9/1933 Ulrich et a1. 260482 2,184,008 12/1939 Dickey et a1 260482 3,144,299 8/1964 Prick et a1.

2,703,810 3/1955 Viard 260482 XR 2,226,202 12/ 1940 Hill et a1. 260482 XR 2,684,381 7/1954 Dial 260482 XR 3,369,858 2/1968 Lourigan et a1. 260--482 XR 3,391,181 7/1968 Scheaerl 260482 FOREIGN PATENTS 309,108 4/1929 Great Britain. 1,030,430 6/ 1953 France.

OTHER REFERENCES Chemical Progress, March 1966 (back cover page).

LORRAINE A. WEINBERGER, Primary Examiner A. P. HALLUIN, Assistant Examiner US Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,524,876 August 18 1970 James E. Gregson, Jr.

certified that error appears in the above identified It is :1 Letters Patent are hereby corrected as patent and that sai shown below:

Column 1, line 15, the formula should appear as RO[CH CH O] fiNI-I Signed and sealed this 2nd day of March 1971.

(SEAL) Attest:

WILLIAM E. SCHUYLER, IR.

Edward M. Fletcher, Jr.

Commissioner of Patents Attesting ()fficer shown below: 

